• <tr id="yyy80"></tr>
  • <sup id="yyy80"></sup>
  • <tfoot id="yyy80"><noscript id="yyy80"></noscript></tfoot>
  • 99热精品在线国产_美女午夜性视频免费_国产精品国产高清国产av_av欧美777_自拍偷自拍亚洲精品老妇_亚洲熟女精品中文字幕_www日本黄色视频网_国产精品野战在线观看 ?

    Adsorption of polyhaloalkane vapors by adaptive macrocycle crystals of WreathArene through C-halogen…π interactions

    2022-06-20 06:20:34ShuNiuLingLingMoHongynXioYongyeZhoChenHoTungLiZhuWuHunCong
    Chinese Chemical Letters 2022年4期

    Shu Niu,Ling-Ling Mo,Hongyn Xio,Yongye Zho,Chen-Ho Tung,Li-Zhu Wu,Hun Cong,*

    a Key Laboratory of Photochemical Conversion and Optoelectronic Materials,Key Laboratory of Bio-inspired Materials and Interfacial Science,Technical Institute of Physics and Chemistry,Chinese Academy of Sciences;School of Future Technology,University of Chinese Academy of Sciences,Beijing 100190,China

    ABSTRACT Polyhaloalkanes are broadly useful yet environmentally harmful stock chemicals,therefore the development of adsorbent materials with capacity and selectivity for polyhaloalkane vapors is highly desirable.Here we report a novel macrocycle WreathArene,a fluorinated C3-symmetrical[16]-paracyclophane.In the crysalline state,WreathArene features guest-adaptive polymorphism for polyhaloalkanes including chloroform,tribromomethane,1,1,2-trichloroethane,and 1,2-dibromoethane.Non-covalent C-halogen…π interactions are observed in all of these host-guest structures.Based on these properties,the activated WreathArene crystals can be utilized as a selective and recyclable adsorbent for polyhaloalkane vapors with excellent capacity under user-friendly conditions.

    Keywords:Macrocycle Paracyclophane Halogen…π Polyhaloalkane Adsorption

    Polyhaloalkanes are important feedstock chemicals with versatile applications including solvents,refrigerants,synthetic reagents,and agrochemicals;however,they are often irritative volatile chemicals which are harmful to environment and health[1].In view of the utility and toxicity of polyhaloalkanes,the development of novel adsorbent materials for polyhaloalkane vapors with desirable selectivity and capacity should have profound potential in areas including chemical reagent purification and pollutant removal[2–11].Recently,nonporous adaptive crystals(NACs)of macrocycles have been a bourgeoning area in supramolecular chemistry for selective adsorption of organic vapors through noncovalent interactions[12–21].Successful NACs thus far are mostly electron-rich macrocyclic arenes which exhibit adsorptive affinity for hydrocarbons through C-H…πinteractions[22–24].Considering the opposite polarities between C-H and C-halogen bonds[25],we speculated that the use of electron-deficient macrocyclic arenes as adsorbents would show preference to polyhaloalkanesviaChalogen…πinteractions.

    C-halogen…πinteractions are relatively weaker in energy compared to other non-covalent interactions,with halogen-centroid distances ranging from 3.3 ?A to 3.8 ?A[26].Although a number of literatures showed their important roles in supramolecular selfassembly and crystal engineering[27–29],C-halogen…πinteractions are less studied in the context of host-guest chemistry of macrocycles[30–33].For instance,halogenated solvent molecules are frequently present,but often neglected,in the crystal structures of macrocycles;and in-depth investigation of C-halogen…πinteractions involving polyhaloalkanes inside macrocyclic cavities would reveal supramolecular properties with potential applications.

    Here we present a novel electron-deficient macrocyclic arene as adaptive crystals exhibiting affinity to polyhaloalkane vapors.This fluorinated neutral macrocycle carries alternatively located perfluorinated and unsubstituted paraphenylene subunits,and is named WreathArene(WA)because its C3-symmetrical shape resembles the popular holiday ornament(Fig.1).Crystal structures of WA with chloroform,tribromomethane(TBM),1,1,2-trichloroethane(TCE)and 1,2-dibromoethane(DBE),respectively,reveal universal C-halogen…πinteractions inside the guest-adaptive cavities of WA.Furthermore,the activated crystals of WA,as an adaptive adsorbent,show selective and recyclable vapor uptake for these polyhaloalkanes under user-friendly conditions.

    Fig 1.The macrocycle WreathArene(WA)and C-halogen…π interactions.

    Fig 2.Synthesis of WreathArene.

    [1n]-Paracyclophanes(PCP)are a class of neutral macrocycles consisting of methylene-bridged paraphenylenes[34].Owing to their structural symmetry and supramolecular properties,[1n]-PCP derivatives have been attractive synthetic targets for decades[35–40].While electron-rich[1n]-PCP are usually prepared using Friedel-Crafts-type reactions[41],new macrocyclization strategy is in need for the fluorinated target molecule.Instead of late-stage functional group manipulations on the macrocycle rims[42–45],our synthesis of WA entails a convergent route which directly constructs the macrocyclic scaffold employing sequential Pd-catalyzed C-H activation processes of fluorinated arenes[46].

    The combination of Pd(OAc)2and PhJohnPhos(L)was optimized to facilitate the key C(sp3)-C(sp2)bond formation between tetrafluorobenzene 1 and benzyl bromide 2.One-pot demethylation/bromination of the coupling product 3 afforded bromide 4 smoothly when treated with BBr3.Various attempts to trimerize 4 directly to the target WA through coupling reactions were unsuccessful.Instead,under the aforementioned optimal coupling conditions,compounds 3 and 4 were converted to 5 and 6,respectively.Similarly,bis(benzyl bromide)7 was obtained from 5viaanother demethylation/bromination step.With both precursors in hand,cross coupling between 6 and 7 furnished the desired macrocyclization,affording WA within four longest linear steps(Fig.2).The concise and convergent synthetic route provides access to this electron-deficient neutral macrocycle in good amount for further study.

    Fig 3.Crystal structure of WA.(a)Top and(b)side view of a single macrocycle.The tetrafluoroparaphenylene subunits are shown in blue.Hydrogen atoms and disordered solvents are omitted for clarity.

    Next,single crystals were obtained by diffusion ofn-pentane into a CHCl3solution of WA.X-ray crystallographic analysis unambiguously confirmed the macrocyclic structure with a slightly distorted hexagonal skeleton(Fig.3).Inside the the crystals,π-πinteractions[47,48]and C-H…F hydrogen bonds[49–51]arrange the hexagonal WA molecules to form parallel honeycomb-like layers with one-dimensional channels(Fig.S18 in Supporting information).Each tetrafluoroparaphenylene subunit always faces an unsubstituted paraphenylene subunit of an adjacent molecule,glued by intra-layerπ-πinteractions.In addition,the parallel layers are neatly stacked in brick-wall-like pattern exhibiting long-range 1D channels which are stabilized by multiple inter-layer C-H…F hydrogen bonds.Such hydrogen bond networks in the solid state would rationalize the "upright" paraphenylene conformations of WA leading to its pillar-like cavity.

    Because of the similar cavity geometries between WA and pillar[6]arenes[52],we reasoned that suitably sized molecules which are rich in high-electronegativity atoms should serve as possible guests for the electron-deficient WA.However,based on a survey of potential guest molecules,we were unsuccessful to identify evident guest inclusion of WA in solution by NMR analysis.This result would likely be linked to the poor solubility of WA:among common organic solvents,WA only dissolves well in dichloromethane and chloroform,both of which provide abundant chlorine atoms surrounding WA,thereby excluding other potential guests.

    In view of the excellent crystallinity of WA,we next investigated its host-guest properties in the solid state.Notably,highly disordered chloroform molecules,which were used as solvent during crystallization,are present inside the macrocyclic cavities of the aforementioned structure of WA crystals(Fig.4a,cf.Fig.3),with C-halogen…πinteractions evidenced by an average chlorinecentroid distance of 3.6 ?A.Encouraged by this observation,we then evaluated other polyhaloalkanes which are in general less investigated as guests for macrocycles.

    Crystallization of WA in mixed solvents of CHCl3and TBM afforded single crystals TBM@WA.With each hexagonal WA occupied by a C3-symmetrical TBM guest at the cavity center,the C-Br bonds pointing to the centeroids of paraphenylenes show an average bromine-centroid distance of 3.5 ?A(Fig.4b).The TBM@WA crystals are almost identical to WA crystallized from CHCl3solutions with regard to molecular packing.Honeycomb-like layers and brick-wall-like stacking were observed which are stabilized by intra-layerπ-πinteractions and inter-layer C-H…F hydrogen bonds,respectively(Fig.S19 in Supporting information).

    Single crystals of TCE@WA and DBE@WA were further obtained respectively by crystallization using the corresponding polyhaloalkane as solvent.Crystallographic analysis revealed the intriguing guest-adaptive features of WA crystals[53],in which the macrocycles adopt relatively more procumbent conformations so that the adaptive cavities could better match the less-symmetrical polyhaloalkane guests.In TCE@WA,a single conformation was observed for the macrocyclic host,the cavity of which is occupied by one TCE molecule of two conformations(Fig.4c).Both conformations maintain staggered with different dihedral angles,and are stabilized by non-covalent C-halogen…πand C-H…πinteractions with WA.With regard to DBE@WA,two conformations for WA were identified with a ratio of 50:50,and each macrocycle could host one DBE molecule within its adaptive cavity assisted by C-halogen…πand C-H…πinteractions(Fig.4d).One of the two macrocycle conformers exclusively pairs DBE guests ofanticonformation.The cavities of the other macrocycle conformer are occupied by two differentgauche-conformations of DBE.

    Fig 4.Crystal structures of polyhaloalkane@WA.(a)CHCl3@WA,(b)TBM@WA,(c)TCE@WA,(d)DBE@WA.The tetrafluoroparaphenylene subunits are shown in blue.Hydrogen atoms of WA are omitted for clarity.

    Similar to TBM@WA,the WA in TCE@WA and DBE@WA pack into honeycomb-like layers,but their more procumbent conformations found in the latter two crystals cause less intra-layerπ-πinteractions(Figs.S20 and S21 in Supporting information).Whereas the presence of multiple inter-layer C-H…F hydrogen bonds can assist to pack the staggered layers into brick-wall-like patterns,longrange channels no longer exist in TCE@WA or DBE@WA.

    Fig.5.(a)PXRD patterns of WA samples:(I)activated WA crystals,(II)after CHCl3 uptake(2 h),(III)after TBM uptake(6 h),(IV)after TCE uptake(2 h),(V)after DBE uptake(3 h).(b)Time-dependent vapor uptake plots.All vapor adsorptions were conducted at 30 °C.

    Based on the non-covalent interactions in the polyhaloalkane@WA crystals,the vapor adsorption capability of WA was explored.WA crystallized from CHCl3/n-pentane was activated by heating under vacuum to remove volatile components.The resulting white powder of activated WA was found crystalline by PXRD,(Fig.5a,sample I),and its patterns match the simulated patterns of the guest-free WA crystals(Fig.S25 in Supporting information).Subsequently,polyhaloalkane vapor uptake experiments confirmed excellent adsorptive capability of WA,which is evidenced by the distinct PXRD pattern changes for all four polyhaloalkanes under evaluation(Fig.5a,samples II-V).After adsorption,the PXRD patterns of WA are consistent with the simulated patterns of the corresponding polyhaloalkane@WA crystal structures(Fig.S25).Such similarities between the experimental and simulated PXRD patterns provide informative insight for solid-vapor adsorptions based on crystal structures.

    By monitoring the vapor uptake kinetics at 30 °C,we established that the adsorption capacities of WA are 0.9,1.0,1.3 and 0.85 in mole ratios(14 wt%,33 wt%,23 wt%,and 21 wt% relative to WA)for chloroform,TBM,TCE,and DBE,respectively.The adsorption rates show positive relationship with the boiling points of the polyhaloalkane guests(Fig.5b).At 30 °C,CHCl3(b.p.61 °C)rapidly reaches saturated adsorption within 20 min,and in parallel experiments,30 min for TCE(b.p.114 °C),2 h for DBE(b.p.131 °C),and 5 h for TBM(b.p.150 °C).Furthermore,time-dependent PXRD monitoring the adsorptive progress of TBM revealed that rapid crystalto-crystal phase transition of WA starts within 5 min of vapor contact(Fig.S26 in Supporting information).

    With single-component adsorption confirmed,we wondered whether WA can serve as a selective adsorbent with preferential affinity to polyhaloalkanes in the presence of other organic vapors.Considering the different volatility of these organic liquids,we defined a preference factor to quantitatively evaluate the selectivity of the competitive mixed-vapor adsorptions.The preference factor of a two-component vapor adsorption equals to the molar ratio of adsorbed vapors divided by the ratio of vapor pressures under the adsorption temperature(Fig.6a).

    Fig 6.Adsorptive preference of WA at 30 °C.(a)The definition of preference factor.(b)Preference factors for competitive adsorptions(2 h)of two-component mixed vapors containing a polyhaloalkane and an organic solvent.(c)Time-dependent vapor uptake of mixed chloroform/ethanol vapors(3:1,v/v).All vapor pressure ratios were calculated using Antoine Equation[54,55].

    The activated WA crystals were subjected to an array of two-component mixed vapors containing a polyhaloalkane and a common organic solvent(Fig.6b).The resulting preference factors exhibit excellent differentiation of polyhaloalkane over nonhalogenated vapors in general.Among the 28 evaluated combinations of two-component mixed vapors,19 combinations show preference factors above 10.The polyhaloalkanes’preference factors follow the trend of TBM>DBE>TCE>CHCl3,indicating the highest affinity for WA toward TBM.The general trend of preference factors for non-halogenated vapors are in the order of CH3CN>EtOH>i-Pr2O>acetone>EtOAc>THF>benzene.

    The commercial chloroform is usually stabilized by doping ethanol(b.p.78 °C)for extended storage to avoid phosgene formation.Single-component evaluations revealed that activated WA crystals can rapidly adsorb chloroform vapor at 30 °C(Fig.5b),whereas no adsorption was observed for ethanol under the same condition(Fig.S33 in Supporting information).Next,adsorptive separation of mixed vapors of CHCl3and ethanol(v/v,3:1 at 30°C)[54,55]showed exclusive adsorption of CHCl3by WA(Fig.6c).Time-dependent vapor uptake indicated that CHCl3reaches saturation within 20 min,similar to the corresponding single-component sorption.

    The recyclability of activated WA crystals was tested by five adsorption-activation cycles of mixed CHCl3and ethanol,and each cycle maintained excellent adsorptive capacity and selectivity(Fig.S35 in Supporting information).According to the PXRD patterns recorded before and after recycling,the crystalline structure of WA could be well preserved(Fig.S36 in Supporting information).

    In summary,we have developed WA,a novel macrocycle featuring C-halogen…πinteractions to host polyhaloalkanes in the crystalline state.Activated guest-free crystals of WA can function as an adaptive and selective adsorbent for polyhaloalkane vapors,exhibiting excellent capability and recyclability.Given that polyhaloalkanes are widely useful yet harmful stock chemicals,the development of macrocycle WA represents a new adaptive adsorbent with future potentials for pollutant removal and energysaving separation.

    Declaration of competing interest

    The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

    Acknowledgments

    Financial support from the National Natural Science Foundation of China(Nos.21672227,21922113,21988102,22071257),Chinese Academy of Sciences(Nos.XDB17000000),the National Key Research and Development Program(No.2017YFA0206903),K.C.Wong Education Foundation,and the TIPC Director’s Fund is gratefully acknowledged.We thank Prof.Congyang Wang(ICCAS),Drs.Xiaodi Yang(Shanghai University of Traditional Chinese Medicine),Jie Su and Wen Zhou(PKU)for the help with compound characterizations.

    Supplementary materials

    Supplementary material associated with this article can be found,in the online version,at doi:10.1016/j.cclet.2021.09.090.

    国产精品二区激情视频| 欧美 日韩 精品 国产| 国产高清videossex| 久久人妻福利社区极品人妻图片| 国产精品1区2区在线观看. | 免费不卡黄色视频| 国产精品av久久久久免费| 亚洲国产毛片av蜜桃av| 又黄又粗又硬又大视频| 狠狠狠狠99中文字幕| 侵犯人妻中文字幕一二三四区| 色综合欧美亚洲国产小说| 麻豆av在线久日| 中文字幕人妻丝袜一区二区| 国产精品影院久久| 又黄又粗又硬又大视频| 亚洲avbb在线观看| 久久久久久久久久久久大奶| 80岁老熟妇乱子伦牲交| 国产无遮挡羞羞视频在线观看| 精品国内亚洲2022精品成人 | 99久久综合精品五月天人人| 在线观看免费日韩欧美大片| 成在线人永久免费视频| 久热这里只有精品99| 亚洲国产欧美日韩在线播放| 亚洲av片天天在线观看| 老司机午夜福利在线观看视频| 最近最新中文字幕大全免费视频| 人妻 亚洲 视频| 久久久精品区二区三区| 精品国产国语对白av| 国产男女内射视频| 亚洲一区二区三区欧美精品| 一二三四社区在线视频社区8| 黄色 视频免费看| 无限看片的www在线观看| 亚洲在线自拍视频| 欧美丝袜亚洲另类 | 国产人伦9x9x在线观看| 人人妻人人澡人人看| 亚洲av熟女| 女性生殖器流出的白浆| 另类亚洲欧美激情| 女人高潮潮喷娇喘18禁视频| 亚洲五月色婷婷综合| 国产激情欧美一区二区| av片东京热男人的天堂| 99国产精品一区二区蜜桃av | 国产男女内射视频| 桃红色精品国产亚洲av| 99精国产麻豆久久婷婷| 亚洲成人免费av在线播放| 精品福利观看| 一级毛片精品| 免费久久久久久久精品成人欧美视频| 视频在线观看一区二区三区| 五月开心婷婷网| 一进一出好大好爽视频| 精品人妻1区二区| 国产精品亚洲一级av第二区| 热re99久久国产66热| 欧美一级毛片孕妇| 大香蕉久久成人网| 精品久久久久久久毛片微露脸| 国产蜜桃级精品一区二区三区 | 美女高潮到喷水免费观看| 国产精品久久久av美女十八| 国产成人欧美| 水蜜桃什么品种好| 美国免费a级毛片| 亚洲色图综合在线观看| 中文字幕av电影在线播放| 大片电影免费在线观看免费| 操美女的视频在线观看| 国产熟女午夜一区二区三区| 最近最新中文字幕大全免费视频| 捣出白浆h1v1| 巨乳人妻的诱惑在线观看| 精品国产亚洲在线| av不卡在线播放| 9色porny在线观看| 老司机福利观看| 国产国语露脸激情在线看| 亚洲色图 男人天堂 中文字幕| 久久99一区二区三区| 美女高潮到喷水免费观看| 99热只有精品国产| 久久亚洲精品不卡| 国产在线观看jvid| 亚洲全国av大片| 9热在线视频观看99| 国精品久久久久久国模美| www.精华液| 人人妻人人澡人人看| 国产精华一区二区三区| 亚洲欧美一区二区三区黑人| 国产一区二区激情短视频| 欧美老熟妇乱子伦牲交| 亚洲少妇的诱惑av| 国产亚洲一区二区精品| 女人爽到高潮嗷嗷叫在线视频| 国产aⅴ精品一区二区三区波| 亚洲综合色网址| 久久久国产成人精品二区 | 色94色欧美一区二区| 少妇被粗大的猛进出69影院| 99国产极品粉嫩在线观看| 国产欧美日韩一区二区三区在线| 国产视频一区二区在线看| 不卡av一区二区三区| 91精品国产国语对白视频| 中文字幕最新亚洲高清| 夜夜夜夜夜久久久久| 69精品国产乱码久久久| 欧美在线一区亚洲| 国产精品自产拍在线观看55亚洲 | 免费在线观看亚洲国产| 欧美日韩成人在线一区二区| 69av精品久久久久久| 成在线人永久免费视频| 19禁男女啪啪无遮挡网站| 国产精品免费一区二区三区在线 | 国产一区二区三区在线臀色熟女 | 在线视频色国产色| 女人被躁到高潮嗷嗷叫费观| 女同久久另类99精品国产91| 国产精品乱码一区二三区的特点 | 精品国产一区二区三区四区第35| 超碰97精品在线观看| 少妇 在线观看| 色婷婷久久久亚洲欧美| 久久 成人 亚洲| 9色porny在线观看| 建设人人有责人人尽责人人享有的| 黄色丝袜av网址大全| av网站在线播放免费| 免费在线观看黄色视频的| 18在线观看网站| 大型av网站在线播放| 男女之事视频高清在线观看| 国产有黄有色有爽视频| 亚洲性夜色夜夜综合| 亚洲中文av在线| 深夜精品福利| 另类亚洲欧美激情| 久久精品aⅴ一区二区三区四区| videos熟女内射| 亚洲精品在线观看二区| 日本五十路高清| 久久久国产欧美日韩av| 男女午夜视频在线观看| 亚洲精品在线观看二区| 男人舔女人的私密视频| 999精品在线视频| 国产视频一区二区在线看| 手机成人av网站| 亚洲色图av天堂| 一边摸一边抽搐一进一出视频| 一本大道久久a久久精品| 老司机深夜福利视频在线观看| 国产成人精品久久二区二区免费| 黄色a级毛片大全视频| av一本久久久久| www.熟女人妻精品国产| 国产日韩一区二区三区精品不卡| 国产精品欧美亚洲77777| 国产精品免费大片| 久久精品国产99精品国产亚洲性色 | 午夜影院日韩av| 亚洲欧美色中文字幕在线| 久久精品熟女亚洲av麻豆精品| 亚洲国产看品久久| 在线观看免费视频网站a站| 久热这里只有精品99| 国产淫语在线视频| 日韩精品免费视频一区二区三区| 在线观看一区二区三区激情| 国产不卡一卡二| 久久中文看片网| 亚洲熟妇中文字幕五十中出 | 精品亚洲成a人片在线观看| 91成人精品电影| 成年动漫av网址| 他把我摸到了高潮在线观看| 国产欧美日韩精品亚洲av| 国产一区二区激情短视频| 久久久国产精品麻豆| 国产亚洲精品久久久久5区| 在线看a的网站| 国产精品久久久久久人妻精品电影| 视频区欧美日本亚洲| 男女之事视频高清在线观看| 女性生殖器流出的白浆| 亚洲精品中文字幕一二三四区| 一级,二级,三级黄色视频| 久久午夜亚洲精品久久| bbb黄色大片| 十分钟在线观看高清视频www| 免费不卡黄色视频| 国产成人欧美在线观看 | 久热爱精品视频在线9| 黑人巨大精品欧美一区二区mp4| 亚洲中文字幕日韩| 日韩欧美国产一区二区入口| 91成人精品电影| 一a级毛片在线观看| 两个人免费观看高清视频| 99在线人妻在线中文字幕 | 久久精品国产99精品国产亚洲性色 | 天天操日日干夜夜撸| 欧美亚洲 丝袜 人妻 在线| 欧美日韩一级在线毛片| 国产区一区二久久| 制服人妻中文乱码| 美女福利国产在线| 99久久99久久久精品蜜桃| 欧美日韩国产mv在线观看视频| 又黄又粗又硬又大视频| 建设人人有责人人尽责人人享有的| 精品国产超薄肉色丝袜足j| 大型黄色视频在线免费观看| 国产亚洲精品第一综合不卡| 午夜福利欧美成人| 亚洲,欧美精品.| 岛国毛片在线播放| 少妇裸体淫交视频免费看高清 | 人人妻人人澡人人爽人人夜夜| 女人久久www免费人成看片| 91成年电影在线观看| 亚洲av熟女| 欧美成狂野欧美在线观看| 三级毛片av免费| 黑人猛操日本美女一级片| 丁香六月欧美| 在线十欧美十亚洲十日本专区| 一边摸一边抽搐一进一出视频| 黑人巨大精品欧美一区二区mp4| 国产一区二区三区视频了| av中文乱码字幕在线| 午夜福利乱码中文字幕| 亚洲av成人av| 国内毛片毛片毛片毛片毛片| 亚洲九九香蕉| 国产精品久久视频播放| 久9热在线精品视频| 久久久国产成人精品二区 | 久久香蕉激情| √禁漫天堂资源中文www| 丁香六月欧美| 国产乱人伦免费视频| 91字幕亚洲| 国产亚洲精品第一综合不卡| 一进一出好大好爽视频| 亚洲人成77777在线视频| 国产黄色免费在线视频| 久久这里只有精品19| 黑人猛操日本美女一级片| 欧美乱码精品一区二区三区| 国产精品1区2区在线观看. | 在线视频色国产色| 国产三级黄色录像| 中亚洲国语对白在线视频| 极品人妻少妇av视频| xxx96com| 午夜福利影视在线免费观看| 老司机在亚洲福利影院| 日韩免费av在线播放| 久久久精品免费免费高清| 成人亚洲精品一区在线观看| 18在线观看网站| 亚洲一区高清亚洲精品| 脱女人内裤的视频| 又紧又爽又黄一区二区| 国产男靠女视频免费网站| 丰满的人妻完整版| 成人免费观看视频高清| 1024视频免费在线观看| 亚洲一区高清亚洲精品| 国产1区2区3区精品| 国产亚洲av高清不卡| 精品亚洲成a人片在线观看| 中文字幕人妻丝袜一区二区| 69av精品久久久久久| 国产成人免费观看mmmm| 国产1区2区3区精品| 天堂俺去俺来也www色官网| 午夜影院日韩av| 人妻一区二区av| 免费观看人在逋| 在线观看免费午夜福利视频| 亚洲avbb在线观看| 韩国av一区二区三区四区| 免费在线观看影片大全网站| 人妻 亚洲 视频| 黄频高清免费视频| 人人妻人人澡人人看| 成人18禁高潮啪啪吃奶动态图| 色综合婷婷激情| 亚洲五月色婷婷综合| 婷婷精品国产亚洲av在线 | 别揉我奶头~嗯~啊~动态视频| 校园春色视频在线观看| 亚洲欧美一区二区三区久久| 婷婷成人精品国产| 成年动漫av网址| 香蕉丝袜av| 久99久视频精品免费| 中文字幕最新亚洲高清| 久久精品亚洲熟妇少妇任你| 男人舔女人的私密视频| 免费在线观看完整版高清| 亚洲五月天丁香| 大片电影免费在线观看免费| 免费在线观看视频国产中文字幕亚洲| 午夜两性在线视频| 热99久久久久精品小说推荐| 在线看a的网站| 国产成人一区二区三区免费视频网站| 国产精品欧美亚洲77777| 久久精品亚洲熟妇少妇任你| 亚洲伊人色综图| 国产一区二区激情短视频| 亚洲色图 男人天堂 中文字幕| 国产成人啪精品午夜网站| 韩国av一区二区三区四区| 身体一侧抽搐| 精品一品国产午夜福利视频| 香蕉丝袜av| 国产麻豆69| 久久国产亚洲av麻豆专区| 999精品在线视频| 国产一卡二卡三卡精品| 免费人成视频x8x8入口观看| 亚洲欧美激情综合另类| 黄色a级毛片大全视频| 在线观看免费视频日本深夜| 巨乳人妻的诱惑在线观看| 叶爱在线成人免费视频播放| 欧美日韩福利视频一区二区| 亚洲情色 制服丝袜| 美女午夜性视频免费| 国产一区二区激情短视频| 国产av又大| 久久热在线av| 老熟妇乱子伦视频在线观看| 亚洲欧美色中文字幕在线| 久久中文字幕人妻熟女| 国产欧美日韩综合在线一区二区| 欧美大码av| 久热爱精品视频在线9| 国产又爽黄色视频| 国产亚洲精品久久久久5区| 亚洲人成伊人成综合网2020| 一区二区三区国产精品乱码| 悠悠久久av| 日本精品一区二区三区蜜桃| 18禁裸乳无遮挡免费网站照片 | 久久久水蜜桃国产精品网| 欧美成狂野欧美在线观看| 伦理电影免费视频| 国产视频一区二区在线看| 久久天堂一区二区三区四区| 黄频高清免费视频| 一进一出抽搐动态| 国产麻豆69| 多毛熟女@视频| 99精品在免费线老司机午夜| 美女国产高潮福利片在线看| 色综合婷婷激情| 亚洲国产欧美日韩在线播放| 高清视频免费观看一区二区| 午夜福利在线观看吧| 免费av中文字幕在线| 欧美不卡视频在线免费观看 | 国产欧美日韩一区二区精品| 精品一区二区三区四区五区乱码| 亚洲国产中文字幕在线视频| 国精品久久久久久国模美| 亚洲一区中文字幕在线| 日韩欧美国产一区二区入口| 一进一出好大好爽视频| 叶爱在线成人免费视频播放| 成人手机av| 亚洲avbb在线观看| 国产成人免费无遮挡视频| 在线观看66精品国产| 欧美av亚洲av综合av国产av| 99热只有精品国产| 久久中文字幕一级| 一区在线观看完整版| 人妻久久中文字幕网| 久久 成人 亚洲| 侵犯人妻中文字幕一二三四区| 少妇粗大呻吟视频| 久久精品国产亚洲av香蕉五月 | 香蕉国产在线看| 老司机福利观看| 热re99久久国产66热| 在线观看免费视频日本深夜| videos熟女内射| 精品乱码久久久久久99久播| 国内毛片毛片毛片毛片毛片| 国产欧美日韩一区二区精品| 欧美中文综合在线视频| 精品国产亚洲在线| 一进一出好大好爽视频| 国产精品九九99| 交换朋友夫妻互换小说| 精品国产一区二区久久| 正在播放国产对白刺激| 91在线观看av| 一区二区三区激情视频| av中文乱码字幕在线| 欧美老熟妇乱子伦牲交| 中文字幕人妻丝袜制服| 99精品久久久久人妻精品| 国产人伦9x9x在线观看| 午夜福利影视在线免费观看| 超碰97精品在线观看| 午夜福利一区二区在线看| 大陆偷拍与自拍| 别揉我奶头~嗯~啊~动态视频| 国产区一区二久久| xxxhd国产人妻xxx| 亚洲五月色婷婷综合| 一二三四在线观看免费中文在| 久久香蕉精品热| 久久国产乱子伦精品免费另类| 人人妻人人澡人人爽人人夜夜| 母亲3免费完整高清在线观看| 成人18禁在线播放| 999精品在线视频| 久久中文看片网| 男女免费视频国产| 色精品久久人妻99蜜桃| 久久久久久亚洲精品国产蜜桃av| 黄色怎么调成土黄色| 亚洲欧美精品综合一区二区三区| 中文字幕制服av| 十八禁网站免费在线| 又大又爽又粗| 欧美一级毛片孕妇| 色播在线永久视频| 精品国产亚洲在线| 欧美午夜高清在线| 久久久久久久久久久久大奶| 久久热在线av| 免费在线观看影片大全网站| 一a级毛片在线观看| 51午夜福利影视在线观看| 午夜成年电影在线免费观看| 国产成+人综合+亚洲专区| 亚洲全国av大片| 久久国产精品大桥未久av| 黑丝袜美女国产一区| 久久这里只有精品19| 欧美午夜高清在线| 叶爱在线成人免费视频播放| 亚洲成a人片在线一区二区| 一区二区三区国产精品乱码| 人人妻,人人澡人人爽秒播| 18禁美女被吸乳视频| 亚洲熟女精品中文字幕| 女警被强在线播放| 两性午夜刺激爽爽歪歪视频在线观看 | 美女高潮到喷水免费观看| 国产色视频综合| 精品国产乱子伦一区二区三区| 午夜两性在线视频| 午夜福利,免费看| 亚洲aⅴ乱码一区二区在线播放 | 久久久久精品人妻al黑| 久久九九热精品免费| 美女扒开内裤让男人捅视频| 欧美 亚洲 国产 日韩一| 大型黄色视频在线免费观看| 午夜影院日韩av| 国产免费现黄频在线看| 如日韩欧美国产精品一区二区三区| 国产亚洲欧美精品永久| 亚洲午夜精品一区,二区,三区| 日韩成人在线观看一区二区三区| 久久国产精品大桥未久av| 十分钟在线观看高清视频www| 99精品在免费线老司机午夜| 热re99久久精品国产66热6| 他把我摸到了高潮在线观看| 久久久久久久精品吃奶| 欧美另类亚洲清纯唯美| 欧美精品啪啪一区二区三区| 欧美在线黄色| 人成视频在线观看免费观看| 成人三级做爰电影| 国产在线一区二区三区精| 男女下面插进去视频免费观看| 夜夜躁狠狠躁天天躁| 午夜免费成人在线视频| 亚洲aⅴ乱码一区二区在线播放 | 亚洲伊人色综图| 久久精品人人爽人人爽视色| 99久久精品国产亚洲精品| 黑人操中国人逼视频| 午夜免费观看网址| 男人操女人黄网站| netflix在线观看网站| 国产又色又爽无遮挡免费看| 久久亚洲真实| 在线av久久热| 亚洲全国av大片| 日韩视频一区二区在线观看| 久久 成人 亚洲| 亚洲欧美色中文字幕在线| 久久精品成人免费网站| 91精品国产国语对白视频| 亚洲 国产 在线| 国内毛片毛片毛片毛片毛片| 女警被强在线播放| 侵犯人妻中文字幕一二三四区| 国产精品久久久人人做人人爽| 男人的好看免费观看在线视频 | 国产成人免费观看mmmm| 精品久久久精品久久久| 丰满的人妻完整版| 精品国产一区二区久久| 91在线观看av| 精品乱码久久久久久99久播| 人人妻人人澡人人看| 精品卡一卡二卡四卡免费| 99在线人妻在线中文字幕 | 久久国产亚洲av麻豆专区| 亚洲精品在线观看二区| av网站免费在线观看视频| 两个人看的免费小视频| 亚洲国产精品合色在线| 人人妻人人爽人人添夜夜欢视频| 大香蕉久久成人网| 99久久99久久久精品蜜桃| av视频免费观看在线观看| 超色免费av| 久久午夜综合久久蜜桃| 一级毛片女人18水好多| ponron亚洲| 黄色视频,在线免费观看| 亚洲成国产人片在线观看| 亚洲成人手机| 免费少妇av软件| 精品免费久久久久久久清纯 | 美女福利国产在线| 国产成人欧美| 国产欧美日韩一区二区精品| 女性被躁到高潮视频| 另类亚洲欧美激情| 制服诱惑二区| 无限看片的www在线观看| 国产av一区二区精品久久| 99精品欧美一区二区三区四区| 久久香蕉激情| 美国免费a级毛片| 一二三四社区在线视频社区8| 国产成人欧美在线观看 | 国产蜜桃级精品一区二区三区 | 国产精品永久免费网站| 十八禁高潮呻吟视频| 一区二区三区精品91| www日本在线高清视频| 亚洲成av片中文字幕在线观看| 桃红色精品国产亚洲av| 色婷婷久久久亚洲欧美| 国产精品二区激情视频| 十分钟在线观看高清视频www| 老汉色∧v一级毛片| 精品免费久久久久久久清纯 | 国产成人精品久久二区二区91| 丁香六月欧美| 精品人妻熟女毛片av久久网站| 一区在线观看完整版| 久久国产精品影院| 亚洲熟妇熟女久久| 成人国语在线视频| 日本黄色视频三级网站网址 | 一边摸一边抽搐一进一小说 | 免费在线观看影片大全网站| 久久国产精品大桥未久av| 久久ye,这里只有精品| avwww免费| 亚洲人成电影免费在线| 热re99久久精品国产66热6| 欧美日韩中文字幕国产精品一区二区三区 | 麻豆乱淫一区二区| 俄罗斯特黄特色一大片| 欧美精品av麻豆av| 精品国产美女av久久久久小说| 久久香蕉激情| 国产精品99久久99久久久不卡| 亚洲av欧美aⅴ国产| 精品国产乱子伦一区二区三区| 宅男免费午夜| 欧美一级毛片孕妇| 精品亚洲成国产av| 欧美成狂野欧美在线观看| 热99国产精品久久久久久7| 国产男女超爽视频在线观看| 亚洲情色 制服丝袜| av中文乱码字幕在线| 精品久久久久久电影网| 麻豆成人av在线观看| 满18在线观看网站| 99国产精品一区二区三区| 老汉色av国产亚洲站长工具| 91大片在线观看| 久久精品熟女亚洲av麻豆精品| 中文字幕人妻熟女乱码| 老熟妇仑乱视频hdxx| 母亲3免费完整高清在线观看|